User-defined keyword spotting (KWS) enables personalized voice interaction by detecting user-specified keywords. A key challenge in this task is distinguishing target keywords from phonetically confusable alternatives. To address this challenge, we propose KFC-KWS, a multimodal framework that leverages connectionist temporal classification (CTC)-guided keyframe selection. Specifically, we exploit the peaky posterior distributions of CTC to identify high-confidence phoneme frames, enabling precise alignment across audio, phoneme, and text modalities. These keyframes are then fused with full-utterance representations through cross-attention to capture both local discriminative cues and global contextual information. On LibriPhrase, KFC-KWS achieves the best-balanced performance (98.73% AUC) and substantially outperforms advanced baselines on the challenging hard subset (97.65% AUC and 7.75% EER), demonstrating its effectiveness in discriminating between highly confusable keywords.